Novel compositions and treatment of textile materials



United States Patent NOVEL COMPOSITIONS AND TREATMENT OF TEXTILE MATERIALS John W. Stewart, Westwood, Mass., assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application February 27, 1953, Serial No. 339,465

28 Claims. (Cl. l17l0) The present invention relates to the finishing of textile materials, and more particularly to a process of producing a durable or stiffened, wrinkle-resistant, finish and/or design on textile fabrics and to novel textile articles or materials. The present invention also relates to a novel composition of matter which is suitable for use in treating textile materials.

It has been suggested heretofore to treat textile fabrics, particularly fabrics of vegetable origin, with an aqueous solution of a vinyl acetate-maleic anhydride copolymer and a polyhydric alcohol such as glycerinc or polyvinyl alcohol and containing sufficient alkali to give a pH above 3.0, and then beat the fabrics at a temperature of 100 C. to 175 C. to provide a wash-rcsistant finish. The fabrics thus produced have a stiffened finish, but the finish is not as permanent as is oftentimes desired, and, in the case of cellulose fabrics, the fabrics do not have satisfactory wrinkle-resistance or crush-resistance.

It has been proposed heretofore to apply alkaline aqueous solutions of a substantially unpolymerized polymethylol melamine or a methyl ether thereof or a substantially unpolymerized dimethylol urea to textile fabrics by impregnation followed by a heat treatment to harden and insolubilize such products in situ in the textile fabric. It has also been proposed to glaze or emboss ccllulosic textile fabrics treated with such products prior to the hardening or insolubilizing step. However, the polymethylol melamines or methyl ethers thereof or the methylol urea products, while they are suitable in many respects, do not impart a finish which is as crisp as is oftentimes desired by the trade. Moreover, when such products are applied to textile materials from acid solutions as partial polymers or colloids and then beat hardened they provide a finish on cellulosic textile materials which is unsatisfactory with respect to wrinkle-resistance or crush-resistance even though some gain in stiffness is obtained.

In accordance with the present invention, it is possible to produce a textile finish or a mechanically-modified textile finish, particularly on cellulosic textile materials, which is not only firmer and more permanent and also more resistant to chlorine pick-up than a finish produced by the use of the thermosetting products described in the preceding paragraph, but also is satisfactory with regard to wrinkle-resistance or crush-resistance. The present invention also provides a novel composition useful for producing such improved finishes on textile materials, and which is quite stable and useful after long periods of storage at room temperatures.

It is one object of this invention to provide a novel composition which is quite stable in storage at normal room temperatures, and which is useful for the treatment of textile materials, particularly cellulosic textile materials, to provide a durable, stiffened and wrinkle-resistant or crush-resistant finish.

It is a further object of this invention to provide a process of treating textile materials, particularly cellulosic textile materials, to produce a crisp or stiffened textile material which is satisfactorily resistant to wrinkling or crushing and which retains such properties after laundering or dry cleaning.

It is a further object of this invention to provide a process of mechanically finishing or mechanically modifying textile fabrics, particularly cellulosic textile fabrics, to provide a crush or wrinkle-resistant, stiffened modified finish or design on the textile fabrics, which finish or design is substantially durable or permanent to washing or dry cleaning.

It is a further object of this invention to provide a finished or mechanically finished textile material, particularly a cellulosic textile material, having a substantially permanent, wrinkle or crush-resistant, stiffened or crisp finish which is highly resistant to laundering or dry cleaning.

Still further objects and advantages of this invention will become apparent from the following description and the appended claims.

The present invention provides a composition comprising a water-soluble methylol imidazolidone-2, a. watersoluble polymeric material containing a plurality of carcarboxylic anhydride groups or carboxyl groups (hereinafter referred to as the polymeric material) as, for example, a water-soluble copolymer of vinyl acetate and maleic anhydride, and a water-soluble polyhydric compound containing at least two hydroxyl groups (hereinafter referred to as the polyhydric compound) as, for example, a water-soluble polyvinyl alcohol or a watersoluble partially hydrolyzed polyvinyl acetate. The composition may be in the form of a dry or substantially dry mixture or in the form of a solution in which the ingredients are dissolved in a solvent, preferably water. Aqueous compositions are preferred, since the methylol imidazolidone-2 is most suitably prepared in the form of an aqueous solution and is readily mixed in such form with the polymeric material and the polyhydric compound or with aqueous solutions thereof to form aqueous compositions which are clear, infinitely dilutable with water and quite stable at ordinary room temperatures. When compositions are prepared in which an organic solvent is employed instead of water, the compositions have a relatively limited period of usefulness. On the other hand, dry or substantially dry compositions are relatively expensive to prepare, although they are quite stable at ordinary room temperatures.

The compositions of this invention may contain varying amounts of the methylol imidazolidone-Z and the combination of the polyhydric compound and the polymeric material, and the proportion of the polyhydric compound to polymeric material in the combination may also be varied appreciably, depending primarily on the specific materials employed and the end use of the composition. In general, satisfactory compositions for most purposes comprise from about 1 to 10 parts by weight of the methylol imidazolidone-Z for each to 1 parts by weight of the combination of the polyhydric compound and the polymeric material, which combination comprises from about 5 to 9 parts by weight of the polymeric material for each 5 to 1 parts by weight of the polyhydric compound. However. when the compositions are to be used as described hereinafter for textile treatment, it is preferred to use compositions comprising from about 1 to 5 parts by weight of the methylol imidazolidone-Z for each 2 to 1 parts by weight of the combination of the polyhydric compound and the polymeric material, which combination comprises from about 6 to 7.5 parts by weight of the polymeric material for each 4 to 2.5 parts by weight of the polyhydric compound.

The above described compositions are soluble in water per se at normal room temperatures, and the pH of the solution formed is below 3.0 and usually between 1.5 and 2.5 depending primarily on the particular polymeric material employed. The aqueous solutions are clear and the methylol imidazolidone-Z therein does not polymerize appreciably at ordinary room temperatures during at least the first week of storage.

Aqueous compositions or organic solvent compositions containing the methylol imidazolidone-2, the polymeric material and the polyhydric compound may be employed for the production of water-resistant coatings or films, although the aqueous compositions are particularly useful for the treatment of textile materials comprising cellulosic fibers or yarns, and are preferred for such use. The compositions may be applied. for example, to a suitable base material such as paper or wood and then dried at room temperature or at a slightly higher temperature to form continuous coatings or films which, though initially soluble in water, may be baked or heated at elevated temperatures to form a water-resistant film or coating which is substantially insoluble in water. Usually, water-resistant films or coatings are obtained by baking or heating the initial films or coatings for periods of l to minutes at temperatures of 225 to 350 F., with the longer period corresponding to the lower temperature, but longer heating periods may also be used. Waterinsoluble films are obtained by baking at temperatures above 250 F.. and preferably between 290 and 375 F. The water-resistant or water-insoluble films or coatings may also he formed by heating the wet films or coatings at temperatures of 225 to 375 F. without preliminary drying.

It is believed that during the baking or heating period the polymeric material reacts or cross-links with the polyhydric compound. and possibly also the methylol imidazolidone-Z, by an esterification reaction with the splitting oil of water or by a direct addition esterification in the case of carboxylic anhydride groups to form a waterinsoluble resinous material which contains at least the polymeric material and the polyhydric compound in a combined state or form. Regardless of the theory involved. however. the fact remains that a water-resistant to water-insoluble resinous material is obtained.

As examples of water-soluble polymeric materials containing a plurality of carboxyl groups and/or carboxylic anhydride groups which may be used in the compositions hereinbefore described may be mentioned the watersoluble copolymers of a polymerizable vinyl or vinylidene compound having a single CH2=C group as, for example, vinyl acetate and ethylenically unsaturated aliphatic dicarboxylic acids or anhydrides containing from 4 to 8 carbon atoms as, for example, maleic anhydride, maleic acid, fumarie acid, itaconic acid, citraconic anhydride, citraconic acid and the like, and mixtures of such dicarboxylic compounds with alkyl half esters of such acids in which the alkyl group contains from i to 4 carbon atoms. as, for example, mixtures of maleic anhydride and methyl acid maleate, or the watersoluble copolymers of vinyl alkyl ethers such as vinyl methyl or ethyl ethers, or methyl vinyl ketone, and such ethylenically unsaturated aliphatic dicarboxylic compounds; or the water'soluble copolymers of mixtures of styrene and vinyl acetate with such ethylenically un saturated aliphatic dicarboxylic compounds. By "watersoluble copolymer" is meant a copolymer which dissolves in water per se with agitation in concentrations of at least 3% by weight at a temperature of F. Of the copolymers described above the water-soluble copolymers of vinyl acetate and maleic anhydride or the watersoluble copolymers of vinyl acetate, maleic anhydride and alkyl half esters of maleic acid in which the alkyl group contains from 1 to 4 carbon atoms, particularly methyl acid maleate, are preferred. In order to obtain highly water-resistant or water-insoluble coatings or textile finishes, it is desirable to employ water-soluble copolymers which have a molecular weight above 500, and preferably above 1000.

As further examples of water-soluble polymeric materials containing a plurality of carboxyl and/or carboxylic anhydride groups which may be used in the compositions of this invention may be mentioned polyitaconic acid, polyitaconic anhydride and the like.

The above copolymers or polymers may be prepared by well-known polymerization procedures. For example, they may suitably be prepared by mass polymerization of the monomers in the presence of a per-oxy polymerization catalyst such as benzoyl peroxide using heat or ultra-violet radiation, or both, to start and complete the polymerization process. The polymeric material is usually obtained in such cases as a solid mass which may be comminuted or ground to form small particles so that the material will dissolve readily in water.

As examples of water-soluble polyhydric compounds containing at least two hydroxyl groups which may be used in the compositions of this invention may be mentioned glycerine, diethylene glycol, ethylene glycol, sorbitol, mannitol, pentaerythritol, water-soluble or waterdispersible forms of starch and the like, and water-soluble polymeric materials containing at least two hydroxyl groups such as polyvinyl alcohol, water-soluble or water dispersible partially hydrolyzed polyvinyl acetates, preferably those in which at least 30% of the acetate groups have been hydrolyzed, water-soluble partially cthcrified polyvinyl alcohols, water-soluble partially esterified polyvinyl alcohols and the like. The polyhydric compound preferably should consist of carbon atoms linked together by carbon to carbon bonds and having only hydrogen and hydroxyl groups attached to such carbon atoms, or preferably should have a molecular weight above 500, or preferably should contain at least 6 hydroxyl groups, or have all of these characteristics. Of the various polyhydric compounds which may be used polyvinyl alcohol provides a superior coating or finish, as compared to other polyhydric alcohols, in so far as permanence and cost are concerned, and, hence, the polyvinyl alcohol is preferred over other polyhydric compounds.

The methylol imidazolidone-Z used in the aqueous compositions of this invention should be substantially the dimethylol imidazolidone-2 and should contain about 1.8 to 2.0 mols of combined formaldehyde per mol of imidazolidone-2. If the amount of combined formaldehyde is appreciably below 2.0 mols, the product tends to polymerize in the composition to a colloidal state and finally polymerizes to such an extent that it precipitates from solution. On the other hand, if the amount of combined formaldehyde in the product is 2 or substantially 2 mols per mol of imidazolidone-Z, the product dissolves in the composition but does not polymerize to any appre ciable extent at normal room temperatures but remains in a monomeric or unpolymerized condition for considerable periods of time and is able to penetrate into fibrous materials because of its low molecular weight and its molecular size. The aqueous compositions remain clear for considerable periods of time indicating the absence of colloidal materials.

The methylol imidazolidone-Z product employed is suitably prepared by contacting imidazolidone-Z with formaldehyde, using about two mols or more of formaldehyde per mol of imidazolidone-2, in an alkaline aqueous solution, preferably at a pH of about 7.5 to 8.5 until a solution of the desired product is obtained. This addition reaction may be carried out at room temperature or at slightly elevated temperatures, for example, 30 to 40 C. The imidazolidone-Z is also known as ethylene urea and has the structural formula:

The aqueous compositions or solutions containing the polymeric material, the polyhydric compound and sub stantially dimethylol imidazolidone-Z are especially useful for the treatment of textile materials, particularly textile materials containing cellulose fibers or yarns, to impart a durable stifi'ened, wrinkle-resistant finish thereto. The textile treating process of this invention is carried out, in general, by applying an aqueous solution having a pH below 3.0, preferably between about 1.5 and 2.8, of the polymeric material. the polyhydric compound and the methylol imidazolidone-Z and, preferably, a curing catalyst, to a textile material such as a cotton or regenerated cellulose fabric as by dipping, spraying or immersion, after which the fabric is dried or partially dried and then heated until a water-insoluble resin or resinous material is formed on the textile material. The baking or heating temperatures and times hereinbefore described may be used and the temperature used should be below the temperature at which the textile material is damaged by heat. The textile material thus obtained has a permanent or substantially permanent or durable stiffened finish which is highly resistant to removal by normal washing or launderinga in aqueous soap or detergent solutions or by dry cleaning, and the finish does not pick up detrimental amounts of chlorine from bleaching solutions. This finish is materially more permanent than finishes prepared by the use of similar solutions, but which have a pH above 3.0. The treated textile material is also resistant to crushing or wrinkling. In order to obtain a textile material having optimum wrinkle-resistance or crush-resistance, it is necessary to treat the fabric before the heating or baking step with a catalyst which is capable of releasing a strong acid during the heating or baking step. This is suitably accomplished by adding the catalyst to the solutions applied to the textile material. The amounts of catalyst used may be varied considerably and satisfactory results are obtained in most cases by using from about 1 to 15% by weight of the catalyst, based on the weight of the methylol imidazolidone-Z employed.

It is believed that during the baking or heating step the polymeric material and the polyhydric compound cross-link or react to form a water-insoluble resinous material or reaction product, whereas the methylol imidazolidone-Z reacts with the textile material, particularly with the hydroxyl groups of cellulose textile materials, to form a chemically modified textile material. irrespective of the theory involved however, the treated textile material is provided with a stiffened, wrinkleresistant finish which is highly durable to laundering or dry cleaning.

As examples of catalysts which may be used may be mentioned ammonium chloride, zinc chloride, monoor diammonium phosphates, salts of hydrochloric or phosphoric acid and a primary amine as, for example, alkyl primary mono-amines such as ethyl amine, propyl amine and the like. salts of hydrochloric or phosphoric acid and a secondary amine as, for example, an alkyl secondary mono-amine such as diethyl amine, dipropyl amine and the like and salts of hydrochloric or phosphoric acid and a hydroxy primary or secondary amine as, for example, an aliphatic primary or secondary mono-amine containing 1 to 4 hydroxyl groups such as mono-ethanolamine, isopropanolamine, l-amino-Z-methyl propanol- 2,4-methyl-4-amino pentanol-Z, diethanolamine, N-methyl, N'-cthanol amine, N-ethyl, N'-ethanol amine, N-di propanediol 1,3 amine and the like. Salts of sulfuric acid and the above described amines may be used, instead of the salts of hydrochloric or phosphoric acid. However, sulfuric acid formed from such salts and remaining in the textile materials, particularly cellulose materials, tends to tender or weaken such materials during the heating or baking step. Consequently, catalysts consisting of salts of sulfuric acid are the least desirable for use in the textile treating processes of this invention.

In general, some wrinkle-resistance and stiffening or crispening effect is obtained on the textile material when as little as 2% by weight of the methylol imidazolidone-2 and 0.25% by weight of the combination of the polymeric material and the polyhydric compound, based on the dry textile material, are applied, although better results are obtained by applying at least 3% by weight of the methylol imidazolidone-Z and at least 1.5% by weight of the combination of the polymeric material and the polyhydric compound. Considerably larger amounts of the methylol imidazolidone-2 and the combination of the polymeric material and the polyhydric compound may be applied to the textile material, for example, as much as 15% by weight of the methylol imidazolidone-Z and 15 or 20% by weight of the combination of the polymeric material and the polyhydric compound, it being also understood, of course, that the larger amounts of methylol imidazolidone-2 may be used with the smaller amounts of the combination of the polymeric material and the polyhydric compound and vice versa. However, for most purposes, it is not necessary to apply more than 10% by weight of the methylol imidazolidone-2 and 5% by weight of the combination of the polymeric material and the polyhydric compound, based on the dry textile material. By increasing the amount of the methylol-imidazolidone-2 applied from 2.0 to 10% the crush or wrinkle-resistance of the textile material is increased. The above described amounts are readily applied to textile materials using an aqueous solution containing from 2 to 15% by weight of the methylol imidazolidone-Z and from 0.25 to 20% by weight of the combination of the polymeric material and the polyhydric compound and adjusting the concentration of these ingredients within such range together with removal of excess solution from the textile material as by squeezing, centrifuging, padding or the like.

The finish produced on the textile material may be modified as to appearance, softness or other properties to some extent, if desired, by incorporating other materials in the aqueous solution which is applied to the textile material. For example, it is possible to incorporate film-forming materials which are soluble in water at a pH below 3.0 as, for example, gelatin and watersoluble forms of starch. It is also possible to incorporate in the treating solution water-soluble thermo setting condensation products of the class of water-soluble condensation products of formaldehyde with urea, thiourea, guanidine, amino triazines having at least two primary amino or amido (-NH2) groups as, for example, melamine, phenyl guanamine, 2-chloro-4,6 diamino-l,3,5 triazine, 2-hydroxy-4,6 diamino-1,3,5 triazine and the like, or water-soluble methyl ethers of such condensation products. Such condensation products enhance the stiffness or crispness of the textile materials but do not improve the crush or wrinkle-resistance of the textile materials to any appreciable extent. When such condensation products are incorporated in the treating solution, the solution, which is initially clear or transparent, becomes milky or cloudy in a relatively short time, varying from about 5 to about minutes depending on the particular condensation product used. This indicates that such condensation product is present in the solution in a colloidal form or state.

The stability of the condensation product employed in the treating solution varies considerably depending primarily on the weight ratio of such condensation product to the combination of the polymeric material and polyhydric compound and the specific condensation product used. For example, when water-soluble methyl ethers of melamine-formaldehyde condensation products and/or water-soluble methyl ethers of urea-formaldehyde condensation products are incorporated in the treating solution in the weight ratio of parts by weight of such condensation product to 1 part by weight of the combination of the polymeric material and the polyhydric compound, milky solutions or dispersions are formed which remain stable for periods of 20 to 24 hours even though the pH of the solution is below 2.8. Under the same conditions the urea-formaldehyde condensation products are less stable and the melamine-formaldehyde condensation products are considerably less stable. As the weight ratio of the combination of the polymeric material and the polyhydric compound to such condensation products in the solution is increased, the solution or dispersion obtained increases in stability, although the solutions of the melamine-formaldehyde or urea-formaldehyde condensation products do not attain the stability of the solutions of the methyl ethers thereof. There is no upper limit to the weight ratio of such combination to the condensation products. However, in most instances. it is preferred to use solutions containing from about 10 to 1 parts by weight of the condensation product for every 1 to it) parts by weight of the combination of the polymeric material and the polyhydric compound. Such solutions are particularly suitable for treating textile materials which are to be mechanically finished as described hereinafter.

It is to be understood, of course. that the condensation products described above are not intended to replace the methylol imidazolidone-2, but may be used in addition to the methylol imidazolidone-Z.

Other materials or additives may be incorporated in the treating solution as, for example. delustering agents such as titanium dioxide, colloidal silica, water-insoluble metallic silicates, talc and diatomaceous earth or the like; and also thickening agents such as gum tragacanth, hydrolyzed starch, alginic acid, hydroxy methyl cellulose, hydroxy ethyl cellulose, gelatin or the like. Normally, the delustering agents are used in amounts below by weight, based on the solid in the solution, whereas the thickening agents are employed in amounts of about 0.5 to 5% by weight of the total composition.

It has presently been found that a substantially permanent or durable, wrinkle-resistant, mechanical finish may be imparted to a textile material, particularly (and preferably) a cellulosic textile fabric such as a cotton or regenerated cellulose fabric, by first applying the aqueous solutions having a pH below 3.0. preferably between 1.5 and 2.5, of the methylol imidazolidone-Z and the combination of the polymeric material and the polyhydric compound or the various modifications of such solutions, hereinbefore described, to the textile material. The textile material is next partially dried, preferably to a moisture content of about 5 to 70% by weight, based on the dry textile material, and is next subjected to a mechanical finishing operation such as calendering, glazing, pleating, crimping, embossing or Schreinering or the like to change the form and relative disposition of the textile fibers or yarns in the textile material and thus alter the surface texture of the textile material. Thereafter, the textile material is heated or baked, preferably at a temperature above 250 F., but below the temperature at which the textile is damaged by heat, until a substantially water-insoluble resin finish is formed on the textile material. This baking or heating step sets the mechanically imparted or modified finish so that the finish remains on the textile material and is substantially permanent to washing and dry cleaning. The permanence or durability of the finish depends primarily on the baking or heating temperatures used, the duration of heating, the specific polymeric material and polyhydric compound employed and the relative amounts of the polymeric material and polyhydric compound applied. In carrying out the above described process it is preferred to employ a mechanical finishing operation in which heat and pressure are applied to the textile material, or to employ heat after mechanical finishing to set the finish on the textile material.

In those instances where a glazed or smooth calendered finish is desired, the textile material may be glazed or smooth calendered before or after the heating or baking step. However, best results are obtained by first applying the solution, partially drying, glazing or smooth calendering and then baking or heating to set the finish, and this procedure is preferred.

When the mechanical finishing is carried out so as to produce a permanent impression, pattern or design on the textile material, this is suitably accomplished by means of rolls which have the desired impression, design or pattern engraved thereon, or by means of engraved platens or the like.

It has been found desirable in the textile treating processes of this invention to immerse the textile material, after the formation of the water-resistant or waterinsoluble resin thereon and after the mechanical finishing, if the latter procedure is used, in an aqueous solution containing alkali-metal or ionizable metal salts such as sodium carbonate, sodium bicarbonate, sodium phosphate, sodium borate, sodium chloride or the corresponding potassium or lithium compounds, and calcium chloride or barium chloride or the like. This treatment may be carried out by agitating the solution, and the solution used may contain convention detergents, if desired. The foregoing treatment has certain advantages, but is not essential for the production of a substantially permanent or durable, wrinkle-resistant, stiffened finish.

In carrying out the embodiment of this invention in which the textile material is mechanically finished, the proportions of the ingredients employed in the aqueous treating solution may be varied to some extent depending on the particular efiect or hand desired. In general, the concentration of the solution and the pick up of the solution by the textile material are adjusted so as to apply about 2 to 15% by weight of the methylol imidazolidone-Z and from about L5 to 15% by weight of the combination of the polymeric material and the polyhydric compound, based on the dry textile material. However, in most instances excellent results are obtained by applying about 3 to 10% by weight of the methylol imidazolidone-Z and from about 1.5 to 5% by weight of the combination of the polymeric material and the polyhydric compound, based on the dry textile material, and the application of such amounts is preferred. To accomplish this, it is possible to employ aqueous solutions containing substantially the same amounts of the methylol imidazolidone-Z and the combination of the polymeric material and polyhydric compound as it is desired to apply to the textile material. The modifying agents such as, for example, the delustering agents, etc. may be incorporated in the treating solution in the proportions hereinbefore described.

The mechanically finished textile materials obtained in accordance with the processes hereinbefore described have a permanent or durable wrinkle-resistant finish which is materially more crisp or stiff, and less chlorine retentive. than the finishes heretofore produced by the use of watersoluble urea-formaldehyde or melamine-formaldehyde condensation products per se.

A further understanding of the compositions, processes and textile products of this invention will be obtained from the following specific examples which are intended to illustrate the invention but not to limit the scope thereof, parts and percentages being by weight unless otherwise specified.

EXAMPLE I (A) Preparation of composition Six parts of a finely divided, water-soluble copolymer of 1 mol of vinyl acetate, 0.8 mol of maleic anhydride and 0.2 mol of methyl acid maleate and three parts of finely divided low viscosity polyvinyl alcohol were first dissolved in 90 parts of water with stirring. After a clear solution Was obtained, 27 parts of a slightly alkaline solution containing 50% by weight of dimethylol imidazolidone-Z were added with stirring until a homogeneous solution was obtained. This solution had a pH of about 2.1 and remained clear and stable for a period of at least one week at a temperature of 75 F. The solution, as initially prepared, was next diluted with water until it contained 3% of dimethylol imidazolidone-2, after which 5% of a 35% aqueous solution of 2-amino-2- methyl propanol-l hydrochloride, based on the dimethylol imidazolidone-2, was added as a catalyst. The resulting solution, which was clear and stable for a considerable period of time at room temperature, was then employed for treating a textile material as described below.

(B) Treatment of a textile material A piece of 80 x 80 cotton fabric was immersed in the composition prepared as described immediately above until it was thoroughly wetted out with the composition, after which the fabric was passed between squeeze rolls to obtain a pick up of 80% of the solution, based on the dry textile material, thus depositing about 4% total solids, based on the dry textile material, of which about 2.4% consisted of dimethylol imidazolidone-2. The fabric was next partially dried until it contained about 15% moisture and was then embossed by passing it between one smooth roll and one engraved roll heated to a temperature of 360 F. using a pressure of about 350 pounds per linear inch. The embossed fabric was then heated at 310 F. until a water-insoluble resinous material was formed on the textile material. The resulting fabric was not only deeply embossed but was also considerably stiffer or crisper and more wrinkle-resistant than the untreated fabric and retained such properties and the embossed design after a number of standard cotton washes or dry cleanings. The fabric did not pick up detrimental amounts of chlorine from bleaching solutions.

EXAMPLE II A piece of 80 x 80 cotton fabric was immersed in an aqueous solution having a pH of about 2.1 (glass electrode) and containing 6% dimethylol imidazolidone-Z, 1.34% of a water-soluble copolymer of 1 mol of vinyl acetate, 0.8 mol of maleic anhydride and 0.2 mol of methyl acid maleate, 0.66% of low viscosity polyvinyl alcohol and 1.75%, based on the dimethylol imidazolidone-2, of 2-amino-2-methyl propanol-l hydrochloride as a catalyst, until the fabric was thoroughly saturated with the solution. The fabric was then passed between squeeze rolls adjusted to give a pick up of 80% of the solution, based on the dry fabric, thus depositing on the fabric about 4.8% of dimethylol imidazolidone-2, about 1.07% of the copolymer and about 0.53% of the polyvinyl alcohol, based on the dry fabric. The treated fabric was next dried for 5 minutes at 200 F. and finally heated for 5 minutes at 300 F. to form a water-insoluble resinous material on the fabric. One-half of the fabric was refinished by washing it for 10 minutes in an aqueous solution of decyl benzene sodium sulfonate, after which the fabric was rinsed twice with water at 100 F. for periods of 10 minutes each and then dried. The resulting fabric is designated fabric (1) in Table 1. The other half of the fabric was given a standard cotton wash in an aqueous solution containing equal amounts of decyl benzene sodium sulfonate and tetra sodium pyrophosphate for a period of 45 minutes at 200 F., after which the fabric was rinsed with water at F. for 5 minutes, rinsed again with water at 140 F. for 10 minutes and finally dried. The resulting fabric is designated fabric (2) in Table l.

A piece of 80 x 80 cotton fabric was treated as described in the preceding paragraph, except that the treating solution contained about 4% of dimethylol imidazolidone-2, 1.34% of a water-soluble copolymer of 1 mol of vinyl acetate, 0.8 mol of maleic anhydride and 0.2 mol of methyl acid maleate, 0.66% of low viscosity polyvinyl alcohol and 1.75%, based on the dimethylol imidazolidone-2, of 2-amino-2-methyl propanol-l hydrochloride as a catalyst. One half of the treated fabric was refinished according to the procedure described in the preceding paragraph and is designated fabric (3) in Table l. The other half of the treated fabric was given a standard cotton wash according to the procedure described in the preceding paragraph, and this fabric is designated fabric (4) in Table 1.

All of the fabrics prepared as described in the two preceding paragraphs, together with a piece of the untreated fabric, were conditioned for 24 hours at a relative humidity of 65% and at a temperature of 70 F. The fabrics were then tested for relative stiffness using a Gurley R. D. stiffness tester of the type described in the patent to Ralph A. Masters, No. 2,092,609, in accordance with the procedure described in such patent, and the fabrics were also tested for relative crush resistance using the testing device and procedure described on pages and 156 of the Technical Manual and Year Book of the American Association of Textile Chemists and Colorists, volume 28 (1952). Table 1 shows the results of these tests, each value representing the average of 10 determinations, 5 of which were made in the warp direction and 5 of which were made in the filling direction of the fabric.

The results set forth in Table 1 indicate that the treated fabrics were significantly stiffer and more wrinkleresistant than the untreated fabric.

EXAMPLE III A 96 x 94 cotton cloth was first immersed in an aqueous solution having a pH of about 2.7 and containing 2.1% of a water-soluble methyl ether of melamine-formaldehyde condensation product, 4% of dimethylol imidazolidone-2, 1.34% of a water-soluble copolymer of 1 mol of vinyl acetate, 0.8 mol of maleic anhydride and 0.2 mol of methyl acid maleate, 0.66% of a low viscosity polyvinyl alcohol and 1.75%, based on the dimethylol imidazolidone-2, of 2-amino-2-methyl propanol-l hydrochloride as a catalyst, until the fabric was thoroughly saturated with the solution. The treating solution had a milky appearance which was believed to be due to the formation of a colloid of the methyl ether of the melamine-formaldehyde condensation product in the solution. The treated fabric was passed between squeeze rolls adjusted to give a pick up of about 80% of the solution, based on the dry fabric weight. The fabric was next dried until it contained approximately 55% moisture and was then embossed or given an ornamental texture by pressing it between two platens having an engraved pattern thereon. The top platen was at a temperature of 350 F. and was forced against the bottom platen at a pressure of 280 pounds per square inch for a period of seconds. The pressure was then released and the fabric was removed from the platens and baked in an oven for 5 minutes at 300 F. to form a waterinsoluble resinous material on the fabric. The fabric thus obtained was stiti and wrinkle-resistant and the embossed pattern of the fabric accurately duplicated the pattern on the platens.

An identical piece of fabric was treated in the manner described in the preceding paragraph with the exception that it was glazed instead of embossed, after partial drying, by passing it through a friction calendar using a pressure of 2000 pounds per linear inch while maintaining the friction roll at a temperature between 300 and 320 F. until a glossy finish was obtained. Finally, the glazed fabric was baked in an oven at 300 F. for 5 minutes to set the finish. The resulting fabric had a durable, stiffened, crush-resistant, lustrous finish.

Both the embossed fabric and the glazed fabric were scoured in a tumbler washer for 45 minutes with soap and soda ash at 200 F. and were then rinsed with water at 200 F. and dried. The finish on the fabric was not appreciably changed by such treatment.

Although the foregoing examples illustrate the treatment of woven cotton fabrics, it is to be understood that the processes of this invention are also applicable to the treatment of fibers, including natural and staple fibers, yarns or filaments and knitted fabrics. For example, the compositions of this invention may be used to impart a durable, crisp or stiffened, wrinkle-resistant finish to fibers or yarns which are then formed or manufactured into fabrics, or cellulosic fibers and yarns may be treated and formed into fabrics which are then mechanically finished as hereinbefore described and finally heated or baked. The processes of this invention which relate to the production of a durable, stiffened, wrinkle-resistant finish per se are applicable to a wide variety of natural and synthetic textile materials including animal textile materials such as wool, camel's hair and the like; natural cellulose textile materials such as cotton, linen, flax and the like; and synthetic textile materials such as nylon, regenerated cellulose, cellulose derivatives such as cellulose acetate and the like. However, such processes are particularly suitable for the treatment of textile materials which normally have poor wrinkle-resistance such as natural cellulose or regenerated cellulose textile materials in order to improve the wrinkle-resistance of such materials. The processes of this invention which relate to the production of mechanically-modified finishes are primarily applicable to the treatment of fabrics composed primarily of cellulosic textile materials such as natural cellulose, regenerated cellulose or cellulose derivatives as, for example, cellulose acetate, preferably fabrics composed primarily of cotton and/or regenerated cellulose.

What is claimed is:

l. A stable composition of matter comprising an aqueous solution of (l) a water-soluble methylol imidazolidone-2 containing 1.8 to 2 mols of combined formaldehyde per mol of imidazolidone-Z, (2) a water-soluble copolymer of (a) a substance selected from the group consisting of polymerizable vinyl and vinylidene compounds having a single CH2=C group and (b) a compound copolymerizable therewith selected from the group consisting of ethylenically unsaturated aliphatic dicarboxylic acids and anhydrides containing from 4 to 8 carbon atoms, and mixtures thereof with alkyl half esters of said acids, in which the alkyl group contains from 1 to 4 carbon atoms. and (3) a water-soluble polyhydric compound consisting of oxygen, carbon and hydrogen atoms, said aqueous solution having a pH below 3.0.

2. A stable composition of matter as in claim I, but further characterized in that said methylol imidazolidone-Z is dimethylol imidazolidone-2 and said copolymer has a molecular weight above 1000.

3. A stable composition of matter comprising an aqueous solution of (l) dimethylol imidazolidone-Z, (2) a water-soluble copolymer of (a) a substance selected from the group consisting of polymerizable vinyl and vinylidene compounds having a single CH2=C group and (b) a compound copolymerizable therewith selected from the group consisting of ethylenically unsaturated aliphatic dicarboxylic acids and anhydrides containing from 4 to 8 carbon atoms, and mixtures thereof with alkyl half esters of said acids, in which the alkyl group contains from 1 to 4 carbon atoms, and (3) a water-soluble polyhydric compound having at least 6 hydroxyl groups, a molecular weight of at least 500 and consisting of carbon atoms linked together by a carbon to carbon bond to which carbon atoms are attached only hydrogen and hydroxyl groups, said aqueous solution having a pH below 3.0 and containing from 10 to 1 parts by weight of (l) for each I to 10 parts by weight of (2) and (3), said copolymer being present in amounts of 5 to 9 parts by weight for each 5 to 1 parts by weight of said polyhydric compound.

4. A composition of matter comprising an aqueous solution of (1) a water-soluble methylol imidazolidone-Z containing 1.8 to 2 mols of combined formaldehyde per mol of imidazolidone-Z, (2) a water-soluble copolymer of (a) a substance selected from the group consisting of polymerizable vinyl and vinylidene compounds having a single CH2=C group and (b) a compound copolyrnerizable therewith selected from the group consisting of ethylenically unsaturated aliphatic dicarboxylic acids and anhydrides containing from 4 to 8 carbon atoms, and mixtures thereof with alkyl half esters of said acids, in which the alkyl group contains from 1 to 4 carbon atoms, 3) a water-soluble polyhydric compound consisting of carbon, oxygen and hydrogen atoms and (4) colloidal particles of a condensation product selected from the class consisting of urea-formaldehyde, thiourea-formaldehyde, guanidine-formaldehyde and formaldehyde-amino-triazine having at least two primary amino groups condensation products and methyl ethers thereof, said aqueous solution having a pH below 3.0.

5. A composition of matter comprising an aqueous solution of (l) dimethylol imidazolidone-Z, 2) a watersoluble copolymer of (a) a substance selected from the group consisting of polymerizable vinyl and vinylidene compounds having a single CH2=C group and (b) a compound selected from the group consisting of ethylenically unsaturated aliphatic dicarboxylic acids and anhydrides containing from 4 to 8 carbon atoms, and mixtures thereof with alkyl half esters of said acids, in which the alkyl group contains from 1 to 4 carbon atoms, (3) a water-soluble polyhydric compound consisting of carbon, oxygen and hydrogen atoms and (4) colloidal particles of a condensation product selected from the class consisting of urea-formaldehyde, thiourea-formaldehyde, guanidineformaldehyde and formaldehyde-amino-triazine having at least two primary amino groups condensation products and methyl ethers thereof, said aqueous solution having a pH below 3.0 and containing from 1 to 10 parts by weight of (4) for each 1 to 10 parts by weight of (2) and (3).

6. A process of finishing textile materials which comprises applying to a textile material a composition comprising an aqueous solution of 1) a water-soluble methylol irnidazolidone-Z containing 1.8 to 2 mols of combined formaldehyde per mol of imidazolidone-Z, (2) a watersoluble copolymer of (a) a substance selected from the group consisting of polymerizable vinyl and vinylidene compounds having a single CH2=C group and (b) a compound copolymerizable therewith selected from the group consisting of ethylenically unsaturated aliphatic dicarboxylic acids and anhydrides containing from 4 to 8 carbon atoms, and mixtures thereof with alkyl half esters of said acids, in which the alkyl group contains from 1 to 4 carbon atoms, and (3) a water-soluble polyhydric compound consisting of carbon, oxygen and hydrogen atoms, said solution having a pH below 3.0, and drying and heating the textile material until a water-insoluble resinous material is formed on the textile material.

7. A process of finishing textile materials composed primarily of cellulose which comprises applying to said textile materials a composition comprising an aqueous solution of (l) a water-soluble methylol imidazolidone-Z containing from 1.8 to 2 mols of combined formaldehyde per mol of imidazolidone-2, (2) a watersoluble copolymer of (a) a substance selected from the group consisting of polymerizable vinyl and vinylidene compounds having a single CH2=C group and (b) a compound copolymerizable therewith selected from the group consisting of ethylenically unsaturated aliphatic dicarboxylic acids and anhydrides containing from 4 to 8 carbon atoms, and mixtures thereof with alkyl half esters of said acids, in which the alkyl group contains from 1 to 4 carbon atoms, and (3) a water-soluble polyhydric compound consisting of carbon, oxygen and hydrogen atoms, said solution having a pH below 3.0, partially drying said textile materials and mechanically finishing said textile materials by the application of pressure to alter the surface texture of the textile materials, said materials being heated at some stage of the process after partial drying until a water-insoluble resinous material is formed on the textile materials.

8. A process of finishing a textile fabric composed primarily of cellulose which comprises applying to said fabric a composition comprising an aqueous solution of (l) dimethylol imidazolidone-Z, (2) a water-soluble copolymer of (a) a substance selected from the group consisting of polymerizable vinyl and vinylidene compounds having a single CH2=C group and (b) a compound copoly merizable therewith selected from the group consisting of ethylenically unsaturated aliphatic dicarboxylic acids and anhydrides, and mixtures thereof with alkyl half esters of said acids, in which the alkyl group contains from 1 to 4 carbon atoms, (3) a water-soluble polyhydric compound consisting of carbon, oxygen and hydrogen atoms and (4) a catalyst for (1), said solution having a pH below 3.0, partially drying said fabric, embossing said fabric and thereafter heating the fabric until a water-insoluble resinous material is formed on the fabric.

9. A process of finishing a textile fabric composed primarily of cellulose which comprises applying to said fabric a composition comprising an aqueous solution of (1) dimethylol imidazolidone-2, (2) a water-soluble copolymer of (a) a substance selected from the group consisting of polymerizable vinyl and vinylidene compounds having a single CH2=C group and (b) a compound copolymerizable therewith selected from the group consisting of ethylenically unsaturated aliphatic dicarboxylic acids and anhydrides thereof containing from 4 to 8 carbon atoms, and mixtures thereof with alkyl half esters of said acids, in which the alkyl group contains from 1 to 4 carbon atoms, and (3) a water-soluble polyhydric compound consisting of carbon, oxygen and hydrogen atoms, said solution having a pH below 3.0, partially drying said fabric, calendering said fabric and subsequently heating said fabric until a water-insoluble resinous material is formed on the fabric.

10. A textile material composed primarily of cellulose and having a stilfened, durable, wrinkleresistant finish comprising a reaction product of a mcthylol imidazolidone-2 containing 1.8 to 2 mols of combined formaldehyde per mol of imidazolidone-Z, and cellulose, and a waterinsoluble reaction product of (l) a water-soluble copolymer of (a) a substance selected from the group consisting of polymerizable vinyl and vinylidene compounds having a single CH2=C group and (b) a compound copolymerizable therewith selected from the group consisting of ethylenically unsaturated aliphatic dicarboxylic acids and anhydrides containing from 4 to 8 carbon atoms, and mixtures hereof with alkyl half esters of said acids, in which the alkyl group contains from l to 4 carbon atoms, and (2) a water-soluble polyhydric compound consisting of carbon, oxygen and hydrogen atoms.

tit

11. A product as claim 10, but further characterized in that the finish is a mechanically-modified texture finish produced by the applicaiton of pressure.

12. A composition as in claim 3, but further characterized in that said copolymer is a water-soluble copolymer of vinyl acetate and maleic anhydride and said polyhydric compound is a water-soluble polyvinyl alcohol.

13. A composition as in claim 3, but further characterized in that said copolymer is a water-soluble copolymer of vinyl acetate, maleic anhydride and an alkyl half ester of maleic acid in which the alkyl group contains from I to 4 carbon atoms and said polyhydric compound is a water-soluble polyvinyl alcohol.

14. A composition as in claim 5, but further characterized in that the copolymer is a water-soluble copolymer of vinyl acetate and maleic anhydride and the polyhydric compound is a water-soluble polyhydric alcohol.

15. A composition as in claim 5, but further characterized in that the copolymer is a water-soluble copolymer of vinyl acetate, maleic anhydride and an alkyl half ester of maleic acid in which the alkyl group contains from 1 to 4 carbon atoms, and the polyhydric compound is a watersoluble polyvinyl alcohol.

16. A process as in claim 6, but further characterized in that the copolymer is a water-soluble copolymer of vinyl acetate and maleic anhydride.

17. A process as in claim 6, but further characterized in that the copolymer is a water-soluble copolymer of vinyl acetate, maleic anhydride and an alkyl half ester of maleic acid in which the alkyl group contains from 1 to 4 carbon atoms.

18. A process as in claim 6, but further characterized in that the solution also contains colloidal particles of a condensation product selected from the class consisting of urea-formaldehyde, formaldchydeaminotriazine having at least two primary amino groups, thiourea-formaldehyde and guanidine-formaldehyde condensation products and methyl ethers thereof.

19. A process as in claim 7, but further characterized in that (2) is a water-soluble copolymer of vinyl acetate and maleic anhydride and (3) is a watensoluble polyvinyl alcohol.

20. A process as in claim 7, but further characterized in that (2) is a water-soluble copolymer of vinyl acetate, maleic anhydride and an alkyl ester of maleic acid in which the alkyl group contains from 1 to 4 carbon atoms and (3) is a water-soluble polyvinyl alcohol.

2]. A process as in claim 7, but further characterized in that the solution also contains from 10 to l parts by weight of colloidal particles of a condensation product selected from the class consisting of urea-formaldehyde, formaldehyde-aminotriazine having at least two primary amino groups, thiourca-t'ormaldehyde and guanidineformaldehyde condensation products and methyl ethers thereof to every 1 to 10 parts by weight of (2) and (3).

22. A process as in claim 8, but further characterized in that (2) is a water'soluble copolymer of vinyl acetate and maleic anhydride and (3) is a water'soluble polyvinyl alcohol.

23. A process as in claim 8, but further characterized in that (2) is a water-soluble copolymer of vinyl acetate. maleic anhydride and an alkyl half ester of maleic acid in which the alkyl group contains from 1 to 4 carbon atoms and (3) is a water-soluble polyvinyl alcohol.

24. A process as in claim 8, but further characterized in that the solution also contains from It) to 1 parts by weight of colloidal particles of a Condensation product selected from the class consisting of urea formaldehyde, iormaldehyde-aminotriazine having at least two primary amino group thiourea-formaldehyde and guani' dine-formaldehyde condensation products and methyl ethers thereof to every t to 10 parts by weight of (2) and (3 25. A process as in claim 9, but furthcr characterized in that the calendering is carried out under heat and pressure.

26. A process as in claim 9, but further characterized in that (2) is a water-soluble copolymer of vinyl acetate and malcic anhydride and (3) is a water-soluble polyvinyl alcohol.

27. A process as in claim 9, but further characterized in that (2) is a water-soluble copolymer of vinyl acetate, maleic anhydride and an alkyl half ester of maleic acid in which the alkyl group contains from 1 to 4 carbon atoms and (3) is a water-soluble polyvinyl alcohol.

28. A process as in claim 9, but further characterized in that the solution also contains from 10 to 1 parts by weight of colloidal particles of a condensation product selected from the class consisting of urea-formaldehyde,

References Cited in the file of this patent UNITED STATES PATENTS Hoover et al. Apr. 10, 1945 Spatt Sept. 2, 1952 OTHER REFERENCES Evans et al.: Abstract of application Serial Number 576,508, published November 1, 1949, 628 O. G. 254. 

10. A TEXTILE MATERIAL COMPOSED PRIMARILY OF CELLULOSE AND HAVING A STIFFENED, DURABLE, WRINKLE-RESISTANT FINISH COMPRISING A REACTION PRODUCT OF A METHYLOL IMIDAZOLIDONE-2 CONTAINING 1.8 TO 2 MOLES OF COMBINED FORMALDEHYDE PER MOL OF IMIDAZOLIDONE-2, AND CELLULOSE, AND A WATERINSOLUBLE REACTION PRODUCT OF (1) A WATER-SOLUBLE COPOLYMER OF (A) A SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF POLYMERIZABLE VINYL AND VINYLIDENE COMPOUNDS HAVING A SINGLE CH2=C< GROUP AND (B) A COMPOUND COPOLYMERIZABLE THEREWITH SELECTED FROM THE GROUP CONSISTING OF ETHYLENICALLY UNSATURATED ALIPHATIC DICARBOXYLIC ACIDS AND ANHYDRIDES CONTAINING FROM 4 TO 8 CARBON ATOMS, AND MIXTURES HEREOF WITH ALKYL HALF ESTERS OF SAID ACIDS, IN WHICH THE ALKYL GROUP CONTAINS FROM 1 TO 4 CARBON ATOMS, AND (2) A WATER-SOLUBLE POLYHYDRIC COMPOUND CONSISTING OF CARBON, OXYGEN AND HYDROGEN ATOMS. 